JP4356564B2 - Laminated recording material - Google Patents
Laminated recording material Download PDFInfo
- Publication number
- JP4356564B2 JP4356564B2 JP2004256565A JP2004256565A JP4356564B2 JP 4356564 B2 JP4356564 B2 JP 4356564B2 JP 2004256565 A JP2004256565 A JP 2004256565A JP 2004256565 A JP2004256565 A JP 2004256565A JP 4356564 B2 JP4356564 B2 JP 4356564B2
- Authority
- JP
- Japan
- Prior art keywords
- recording material
- laminated
- laminated recording
- layer
- material according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims description 79
- 239000010410 layer Substances 0.000 claims description 60
- 238000004040 coloring Methods 0.000 claims description 39
- 239000011241 protective layer Substances 0.000 claims description 37
- 239000011248 coating agent Substances 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- RRJHFUHAKCSNRY-UHFFFAOYSA-L [Cu+2].[O-]P([O-])=O Chemical compound [Cu+2].[O-]P([O-])=O RRJHFUHAKCSNRY-UHFFFAOYSA-L 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 14
- 229910010272 inorganic material Inorganic materials 0.000 claims description 12
- 239000011147 inorganic material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 8
- DHGSSULXZRNIPW-UHFFFAOYSA-L copper;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Cu+2].[O-]P([O-])(=O)C1=CC=CC=C1 DHGSSULXZRNIPW-UHFFFAOYSA-L 0.000 claims description 7
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
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- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 3
- GKZPEYIPJQHPNC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GKZPEYIPJQHPNC-UHFFFAOYSA-N 0.000 description 3
- JRJNSEMUYTUGLA-UHFFFAOYSA-N 3-phenoxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC1=CC=CC=C1 JRJNSEMUYTUGLA-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
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- 239000004698 Polyethylene Substances 0.000 description 3
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- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
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- 239000004645 polyester resin Substances 0.000 description 3
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- 238000012805 post-processing Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- ABJAMKKUHBSXDS-UHFFFAOYSA-N 3,3-bis(6-amino-1,4-dimethylcyclohexa-2,4-dien-1-yl)-2-benzofuran-1-one Chemical compound C1=CC(C)=CC(N)C1(C)C1(C2(C)C(C=C(C)C=C2)N)C2=CC=CC=C2C(=O)O1 ABJAMKKUHBSXDS-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 229910009372 YVO4 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- 239000002518 antifoaming agent Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
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- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
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- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
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- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- CRPRCSYCZWFVED-UHFFFAOYSA-N (4-ethylphenyl)phosphonic acid Chemical compound CCC1=CC=C(P(O)(O)=O)C=C1 CRPRCSYCZWFVED-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- VKGPHIUFTMBVRL-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate;2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C.C=CC(=O)OCCOCCOC(=O)C=C VKGPHIUFTMBVRL-UHFFFAOYSA-N 0.000 description 1
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- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
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- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- HHKAGFTWEFVXET-UHFFFAOYSA-N 2-heptyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CCCCCCCC(CO)(CO)CO HHKAGFTWEFVXET-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical class C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- ROPDSOYFYJCSTC-UHFFFAOYSA-N 2-phenoxyundecyl prop-2-enoate Chemical compound CCCCCCCCCC(COC(=O)C=C)OC1=CC=CC=C1 ROPDSOYFYJCSTC-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- TWZKDAKZQWRPBJ-UHFFFAOYSA-N 3,3-bis[4-(dimethylamino)phenyl]-6-nitro-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C([N+]([O-])=O)C=C2C(=O)O1 TWZKDAKZQWRPBJ-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- 229940073735 4-hydroxy acetophenone Drugs 0.000 description 1
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- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
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- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- CGEXUOTXYSGBLV-UHFFFAOYSA-N phenyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OC1=CC=CC=C1 CGEXUOTXYSGBLV-UHFFFAOYSA-N 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Description
本発明は、感熱発色層及び表面保護層を有する積層記録材およびこれを用いた感熱記録方法に関する。 The present invention relates to a laminated recording material having a thermosensitive coloring layer and a surface protective layer, and a thermosensitive recording method using the same.
近頃、飲料缶、飲料容器、化粧品容器、医薬品容器、或いは電子部品、電気部品、電気製品、自動車部品、シート、カードなどの表面に製造年月日、賞味期限、製造会社名、製品名、シリアル番号などを明記する方法として、非接触で且つマーキング速度が速く、幅広い素材の表面形状にとらわれることなくマーキング可能であり、自動化、工程管理が容易な、レーザーマーキングが普及している。また、レーザーマーキングは、素材自身に直接マーキングするため、溶剤を含む通常のインキを使わず済み、そのため環境的にもクリーンなマーキング方法として最近注目を受けている。 Recently, on the surface of beverage cans, beverage containers, cosmetic containers, pharmaceutical containers, or electronic parts, electrical parts, electrical products, automobile parts, sheets, cards, etc., the date of manufacture, expiration date, manufacturer name, product name, serial As a method for clearly specifying a number, laser marking, which is non-contact, has a high marking speed, can be marked without being constrained by the surface shape of a wide range of materials, and is easy to automate and process control, is widely used. In addition, since the laser marking directly marks the material itself, it is not necessary to use a normal ink containing a solvent. Therefore, the laser marking has recently received attention as an environmentally clean marking method.
現在、使用されているレーザーマーキングは、樹脂や金属などに直接レーザーを照射することにより、照射部分が熱分解したり蒸発することによって表面に物理的変化を生じさせたり、発色または脱色させることでマーキングする仕組みである。しかし、幅広い用途で使用されている樹脂をマーキングする場合、樹脂自身はレーザーの種類により多少の差はあるもののレーザー感度が低いためマーキングは困難である。特に、それらの樹脂は、大出力でありながら微細加工ができるＹＡＧレーザー光の波長１０６４ｎｍに対してはほとんど感度を持たない。
このような問題に対して、レーザー感度を持ちながら熱で変色する無機素材を一緒に樹脂に添加し、樹脂成型物のレーザーマーキング性を向上させることが行われている。
Currently, laser marking is used by directly irradiating a resin, metal, etc. with a laser, causing the irradiated part to thermally decompose or evaporate, causing physical changes on the surface, and coloring or decoloring. It is a marking mechanism. However, when marking resins used in a wide range of applications, marking is difficult because the resin itself has low differences in laser sensitivity, although there are some differences depending on the type of laser. In particular, these resins have little sensitivity to a wavelength of 1064 nm of YAG laser light that can be finely processed while having high output.
In order to solve such a problem, an inorganic material that changes color with heat while having laser sensitivity is added to the resin together to improve the laser marking property of the resin molding.
最近では、カード、容器等、厚みのある樹脂成型体へのレーザーマーキングの他、フイルム、シートといった折れ曲がりが可能な薄層形状体にもレーザーマーキングが展開されつつある。この場合、塗工により感熱発色層を形成することが多いため、一般的に感熱発色層の厚みが薄く、印字、描画した場合、コントラストが不鮮明であったり、感熱発色層を塗工後、そのまま印字した場合、加熱時の熱、発生ガス等で印字表面の形状が歪になる問題があった。また、その場合、後加工による印字表面の保護がないと実用性のある耐水性、耐油性、耐摩擦性、耐久性は得られなかった。 Recently, in addition to laser marking on thick resin moldings such as cards and containers, laser marking is being developed for thin-layered bodies such as films and sheets that can be bent. In this case, since the thermosensitive coloring layer is often formed by coating, the thickness of the thermosensitive coloring layer is generally thin, and when printed or drawn, the contrast is unclear or the thermosensitive coloring layer is applied as it is after coating. In the case of printing, there is a problem that the shape of the printing surface is distorted by heat during heating, generated gas, and the like. In that case, practical water resistance, oil resistance, friction resistance, and durability could not be obtained without protection of the print surface by post-processing.
紙基材の場合は、レーザーマーキングに使用されている波長では紙基材に対して吸収を持たないため直接マーキングは困難である。そのため実際にはレーザー感度を有する感熱発色層を紙基材上に形成させてマーキングを行う方法や、更にレーザー感度を向上させるためにアルミニウムの蒸着等で反射層を形成することも開示されている。
紙基材へレーザーマーキングする場合も塗工により感熱発色層を形成することが多いため、一般的に感熱発色層の厚みが薄く、更に塗工液が紙基材へ浸透し易い。そのため印字、描画した場合、コントラストが不鮮明になる問題があった。また、その場合、後加工による印字表面の保護がないと実用性のある耐水性、耐油性、耐摩擦性、耐久性は得られなかった。 Also in the case of laser marking on a paper substrate, since the thermosensitive coloring layer is often formed by coating, the thickness of the thermosensitive coloring layer is generally thin, and the coating liquid is likely to penetrate into the paper substrate. Therefore, there is a problem that the contrast becomes unclear when printed or drawn. In that case, practical water resistance, oil resistance, friction resistance, and durability could not be obtained without protection of the print surface by post-processing.
そこで、本発明は、感熱による発色において、印字、描画が鮮明であり、耐久性に優れ、コントラストの高い黒色発色を示す記録材、およびその記録方法を提供することを目的とする。 SUMMARY OF THE INVENTION An object of the present invention is to provide a recording material that has clear printing and drawing in heat-sensitive color development, has excellent durability, and exhibits high-contrast black color development, and a recording method therefor.
即ち、本発明は、感熱発色層及び表面保護層を有する積層記録材に関する。
また、本発明は、感熱発色層が芳香環を有するホスホン酸銅および担持体を含有することを特徴とする上記積層記録材に関する。
また、本発明は、感熱発色層が、無機材料、カーボンブラックまたはグラファイトから選ばれる一種以上の材料を含有することを特徴とする上記積層記録材に関する。
また、本発明は、芳香環を有するホスホン酸銅が、フェニルホスホン酸銅であることを特徴とする上記積層記録材に関する。
また、本発明は、無機材料が、銅原子を含有することを特徴とする上記積層記録材に関する。
また、本発明は、接着剤層若しくはアンカーコート剤層を有することを上記積層記録材に関する。
また、本発明は、感熱発色層が食品包装用積層体と一体となって形成されることを特徴とする上記積層記録材に関する。
また、本発明は、担持体がウレタン樹脂であることを特徴とする上記積層記録材に関する。
That is, the present invention relates to a laminated recording material having a thermosensitive coloring layer and a surface protective layer.
The present invention also relates to the above-mentioned laminated recording material, wherein the thermosensitive coloring layer contains a copper phosphonate having an aromatic ring and a support.
The present invention also relates to the above-mentioned laminated recording material, wherein the thermosensitive coloring layer contains one or more materials selected from inorganic materials, carbon black and graphite.
The present invention also relates to the above laminated recording material, wherein the copper phosphonate having an aromatic ring is copper phenylphosphonate.
The present invention also relates to the above laminated recording material, wherein the inorganic material contains a copper atom.
The present invention also relates to the laminated recording material having an adhesive layer or an anchor coating agent layer.
The present invention also relates to the above-mentioned laminated recording material, wherein the thermosensitive coloring layer is formed integrally with the food packaging laminate.
The present invention also relates to the above laminated recording material, wherein the carrier is a urethane resin.
さらに、本発明は、表面保護層が放射線硬化性であることを特徴とする上記積層記録材に関する。
さらに、本発明は、表面保護層をなす放射線硬化モノマーのうち、３官能以上のモノマーが２０〜９５重量％であることを特徴とする上記積層記録材に関する。
さらに、本発明は、表面保護層がイソシアネートで硬化されることを特徴とする上記積層記録材に関する。
さらに、本発明は、基材層を有する上記積層記録材に関する。
さらに、本発明は、記録材の基材が紙であることを特徴とする上記積層記録材に関する。
さらに、本発明は、記録材の基材がプラスチックであることを特徴とする上記積層記録材に関する。
加えて、本発明は、上記積層記録材を加熱により記録することを特徴とする感熱記録方法に関する。
加えて、本発明は、感熱発色が、サーマルヘッドまたはレーザー光により行なわれることを特徴とする上記感熱記録方法に関する。
Furthermore, the present invention relates to the above-mentioned laminated recording material, wherein the surface protective layer is radiation curable.
Furthermore, the present invention relates to the above-mentioned laminated recording material, wherein among the radiation curable monomers forming the surface protective layer, the tri- or higher functional monomer is 20 to 95% by weight.
Furthermore, the present invention relates to the above-mentioned laminated recording material, wherein the surface protective layer is cured with isocyanate.
Furthermore, the present invention relates to the above laminated recording material having a base material layer.
Furthermore, the present invention relates to the above-mentioned laminated recording material, wherein the base material of the recording material is paper.
Furthermore, the present invention relates to the above-mentioned laminated recording material, wherein the recording material base material is plastic.
In addition, the present invention relates to a heat-sensitive recording method characterized by recording the laminated recording material by heating.
In addition, the present invention relates to the above thermal recording method, wherein the thermal coloring is performed by a thermal head or laser light.
本発明の積層記録材は、感熱により鮮明な印字性、描画性を有するため、通常の印刷インキなみの印字品質を提供できる。また、表面保護層があるため印字後の後加工なしに、優れた耐水性、耐油性、耐摩耗性を示す。更に、感熱発色層に感熱発色性の優れたホスホン酸銅使用することで、コントラストが鮮明な画像を記録でき、かつ表面保護層を設けることで記録材として耐久性が良好な積層記録材を提供することが可能となった。
また、本発明の感熱発色層および表面保護層を有する積層記録材を用いた感熱記録方法によれば、安定した濃度・色彩をもつコントラストの高い感熱記録をすることができる。
Since the laminated recording material of the present invention has clear printability and drawing performance due to heat sensitivity, it can provide print quality similar to ordinary printing ink. In addition, since it has a surface protective layer, it exhibits excellent water resistance, oil resistance, and abrasion resistance without post-processing after printing. In addition, the use of copper phosphonate with excellent thermochromic properties in the thermosensitive color-developing layer enables recording of images with a clear contrast and the provision of a surface protective layer to provide a laminated recording material with good durability as a recording material. It became possible to do.
Further, according to the thermal recording method using the laminated recording material having the thermal coloring layer and the surface protective layer of the present invention, thermal recording with high contrast and stable density and color can be performed.
まず、感熱発色層について説明する。感熱発色層としては
１）感熱記録において使用される公知の発色剤、及顕色剤
２）芳香環を有するホスホン酸銅
を使用することができる。
発色剤としては感熱記録において電子供与体として使われている発色性化合物が使用できる。例えば、フルオラン系、フェノチアジン系、スピロピラン系、トリフェニルメタフタリド系、ローダミンラクタム系等のロイコ染料が挙げられる。ロイコ染料の具体例としては、３，３−ビス（ｐ−ジメチルアミノフェニル）フタリド、３，３−ビス（ｐ−ジメチルアミノフェニル）−６−ジメチルアミノフタリド、３，３−ビス（ｐ−ジメチルアミノフェニル）−６−アミノフタリド、３，３−ビス（ｐ−ジメチルアミノフェニル）−６−ニトロフタリド、３，３−ビス（ｐ−ジメチルアミノフェニル）フタリド、３，３−ビス（３−ジメチルアミノ）−７−メチルフルオラン、３−ジエチルアミノ−７−クロロフラン、３−ジエチルアミノ−６−クロロ−７−メチルフルオラン、３−ジエチルアミノ−７−アニリノフルオラン、３−ジエチルアミノ−６−メチル−７−アニリノフルオラン、３−ピペリジノ−６−メチル−７−アニリノフルオラン等が挙げられる。
First, the thermosensitive coloring layer will be described. As the heat-sensitive color developing layer, 1) a known color former used in heat-sensitive recording, and a developer, and 2) copper phosphonate having an aromatic ring can be used.
As the color former, a color developable compound used as an electron donor in thermal recording can be used. For example, leuco dyes such as fluorane, phenothiazine, spiropyran, triphenylmethphthalide, rhodamine lactam and the like can be mentioned. Specific examples of the leuco dye include 3,3-bis (p-dimethylaminophenyl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, and 3,3-bis (p- Dimethylaminophenyl) -6-aminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-nitrophthalide, 3,3-bis (p-dimethylaminophenyl) phthalide, 3,3-bis (3-dimethylamino) ) -7-methylfluorane, 3-diethylamino-7-chlorofuran, 3-diethylamino-6-chloro-7-methylfluorane, 3-diethylamino-7-anilinofluorane, 3-diethylamino-6-methyl- Examples include 7-anilinofluorane and 3-piperidino-6-methyl-7-anilinofluorane.
顕色剤としては、感熱記録体において電子受容体として使用される物質、例えばフェノール系化合物である４−フェニルフェノール、４−ヒドロキシアセトフェノン、２，２−ジヒドロキシジフェニル、２，２−メチレンビス（４−クロロフェノール）、２，２−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、４，４−イソプロピリデンジフェノール、４，４−イソプロピリデンビス（２−クロロフェノール）、４，４−イソプロピリデンビス（２−メチルフェノール）、４，４−エチレンビス（２−メチルフェノール）等、その他酸性白土カオリン、ゼオライト、芳香族カルボン酸、その無水物、有機スルホン酸を用いることができる。なかでもフェノール系化合物が好ましい。
発色剤と顕色剤の比率は、発色剤１重量部に対して、顕色剤２〜１０重量部が好ましい。また、発色剤と顕色剤の合計が感熱発色層中で占める割合は３０〜９０重量％であることが好ましい。
As the developer, a substance used as an electron acceptor in a heat-sensitive recording material, such as 4-phenylphenol, 4-hydroxyacetophenone, 2,2-dihydroxydiphenyl, 2,2-methylenebis (4- Chlorophenol), 2,2-methylenebis (4-methyl-6-tert-butylphenol), 4,4-isopropylidenediphenol, 4,4-isopropylidenebis (2-chlorophenol), 4,4-isopropylidene Bis (2-methylphenol), 4,4-ethylenebis (2-methylphenol), and other acidic clay kaolin, zeolite, aromatic carboxylic acid, its anhydride, and organic sulfonic acid can be used. Of these, phenol compounds are preferred.
The ratio between the color former and the developer is preferably 2 to 10 parts by weight with respect to 1 part by weight of the color developer. Further, the ratio of the total of the color former and the developer in the thermosensitive color developing layer is preferably 30 to 90% by weight.
本発明に使用される感熱発色層は、上記発色剤、顕色剤の他、スルホン酸エステル類、スルホン酸アミド類、ジフェニルスルホン酸類、ナフトール誘導体類、尿素誘導体類等の増感剤、活性剤、紫外線吸収剤、消泡剤、着色剤等も必要に応じて使用できる。 In addition to the above color former and developer, the thermosensitive coloring layer used in the present invention is a sensitizer such as a sulfonic acid ester, a sulfonic acid amide, a diphenylsulfonic acid, a naphthol derivative, a urea derivative or the like, an activator. In addition, ultraviolet absorbers, antifoaming agents, coloring agents, and the like can be used as necessary.
本発明の一つをなす芳香環を有するホスホン酸銅は、記録時の温度で酸化反応を起こしやすく、非常に着色力の高い黒色または褐色に発色するものである。例えば、フェニルホスホン酸銅、２−メトキシフェニルホスホン酸銅、４−メトキシフェニルホスホン酸銅、４−エチルフェニルホスホン酸銅、２−イソプロピルフェニルホスホン酸銅、３−ニトロフェニルホスホン酸銅、４−ニトロフェニルホスホン酸銅、２−メチル−４−ニトロフェニルホスホン酸銅、３−メチル−５−ニトロフェニルホスホン酸銅、２−クロロ−５−メチルフェニルホスホン酸銅、４−クロロフェニルホスホン酸銅、４−ブロモフェニルホスホン酸銅、２−ヨードフェニルホスホン酸銅、２−フルオロフェニルホスホン酸銅等が挙げられる。特に、フェニルホスホン酸銅は、高い耐熱性および樹脂などへの分散性が良好であり、また安価に合成できるため好ましい。芳香環を有するホスホン酸銅は、二種類以上を混合して用いてもよい。その他の感熱による発色剤としては、銅、モリブデンの複合酸化物（トマテック４２−９００Ａ、東缶マテリアル・テクノロジー株式会社製）、ＡＴＯドープマイカ等が挙げられる。 The copper phosphonate having an aromatic ring which constitutes one of the present invention easily causes an oxidation reaction at the temperature at the time of recording, and develops a black or brown color with very high coloring power. For example, copper phenylphosphonate, copper 2-methoxyphenylphosphonate, copper 4-methoxyphenylphosphonate, copper 4-ethylphenylphosphonate, copper 2-isopropylphenylphosphonate, copper 3-nitrophenylphosphonate, 4-nitro Copper phenylphosphonate, copper 2-methyl-4-nitrophenylphosphonate, copper 3-methyl-5-nitrophenylphosphonate, copper 2-chloro-5-methylphenylphosphonate, copper 4-chlorophenylphosphonate, 4- Examples include copper bromophenylphosphonate, copper 2-iodophenylphosphonate, copper 2-fluorophenylphosphonate. In particular, copper phenylphosphonate is preferable because it has high heat resistance and good dispersibility in resins and can be synthesized at low cost. Two or more kinds of copper phosphonate having an aromatic ring may be mixed and used. Other heat-sensitive color formers include copper and molybdenum composite oxides (TOMATECH 42-900A, manufactured by Tocan Material Technology Co., Ltd.), ATO-doped mica, and the like.
感熱発色層には、記録時の熱伝導性や、熱源としてレーザー光を用いる場合のレーザー光に対する感度を向上させるため、無機材料、カーボンブラックまたはグラファイトから選ばれる一種以上の材料を含有させることが好ましい。無機材料、カーボンブラック、グラファイトは、二種類以上を混合して用いてもよい。また、芳香環を有するホスホン酸銅と、無機材料、カーボンブラックまたはグラファイトから選ばれる一種以上の材料の混合重量比率は、９９．９：０．１〜１０：９０が好ましく、その範囲の中でも９５：５〜５０：５０がより好ましい。 The thermosensitive coloring layer may contain one or more materials selected from inorganic materials, carbon black, and graphite in order to improve thermal conductivity during recording and sensitivity to laser light when using laser light as a heat source. preferable. Two or more inorganic materials, carbon black, and graphite may be used in combination. In addition, the mixing weight ratio of the copper phosphonate having an aromatic ring and one or more materials selected from inorganic materials, carbon black, and graphite is preferably 99.9: 0.1 to 10:90, and within that range, 95 : 5 to 50:50 is more preferable.
無機材料としては、金属の単体、塩、酸化物、水酸化物等を用いることができる。
金属の単体として具体的には、鉄、亜鉛、スズ、ニッケル、銅、銀、金等が挙げられる。
金属の塩として具体的には、炭酸カルシウム、炭酸銅、炭酸ニッケル、炭酸マンガン、炭酸コバルト、炭酸ランタン、硝酸マグネシウム、硝酸マンガン、硝酸鉄、硝酸カドミウム、硝酸亜鉛、硝酸コバルト、硝酸鉛、硝酸ニッケル、硝酸銅、硝酸パラジウム、硝酸ランタン、酢酸マグネシウム、酢酸マンガン、酢酸カドミウム、酢酸亜鉛、酢酸コバルト、酢酸鉛、酢酸ニッケル、酢酸銅、酢酸パラジウム、塩化銅、塩化鉄、塩化コバルト、塩化ニッケル、塩化銀、塩化亜鉛、リン酸銅、リン酸鉄、リン酸コバルト、ピロリン酸銅、硫酸銅、硫酸鉄、硫酸コバルト、シュウ酸銅、シュウ酸鉄、シュウ酸コバルト、安息香酸銅、安息香酸鉄、安息香酸コバルト等が挙げられる。
As the inorganic material, a simple metal, salt, oxide, hydroxide or the like can be used.
Specific examples of the simple metal include iron, zinc, tin, nickel, copper, silver, and gold.
Specific examples of metal salts include calcium carbonate, copper carbonate, nickel carbonate, manganese carbonate, cobalt carbonate, lanthanum carbonate, magnesium nitrate, manganese nitrate, iron nitrate, cadmium nitrate, zinc nitrate, cobalt nitrate, lead nitrate, nickel nitrate , Copper nitrate, palladium nitrate, lanthanum nitrate, magnesium acetate, manganese acetate, cadmium acetate, zinc acetate, cobalt acetate, lead acetate, nickel acetate, copper acetate, palladium acetate, copper chloride, iron chloride, cobalt chloride, nickel chloride, chloride Silver, zinc chloride, copper phosphate, iron phosphate, cobalt phosphate, copper pyrophosphate, copper sulfate, iron sulfate, cobalt sulfate, copper oxalate, iron oxalate, cobalt oxalate, copper benzoate, iron benzoate, And cobalt benzoate.
金属の酸化物として具体的には、酸化ケイ素、酸化チタン、酸化アルミニウム、酸化鉄、酸化マグネシウム、酸化亜鉛、酸化コバルト、酸化鉛、酸化スズ、酸化アンチモン、酸化インジウム、酸化マンガン、酸化モリブテン、酸化ニッケル、酸化銅、酸化パラジウム、酸化ランタン、アンチモンドープ酸化スズ（ＡＴＯ）、インジウムドープ酸化スズ（ＩＴＯ）、合成ゼオライト、天然ゼオライト、銅−モリブテン複合酸化物等が挙げられる。金属酸化物としては、層状構造を有する、マイカ、モンモリロナイト、スメクタイト、タルク、クレー等を用いることもできる。 Specific examples of metal oxides include silicon oxide, titanium oxide, aluminum oxide, iron oxide, magnesium oxide, zinc oxide, cobalt oxide, lead oxide, tin oxide, antimony oxide, indium oxide, manganese oxide, molybdenum oxide, and oxide. Examples thereof include nickel, copper oxide, palladium oxide, lanthanum oxide, antimony-doped tin oxide (ATO), indium-doped tin oxide (ITO), synthetic zeolite, natural zeolite, and copper-molybten complex oxide. As the metal oxide, mica, montmorillonite, smectite, talc, clay and the like having a layered structure can also be used.
金属の水酸化物として具体的には、水酸化銅、水酸化アルミニウム、水酸化マグネシウム、水酸化亜鉛、水酸化アンチモン、水酸化コバルト、水酸化ニッケル、水酸化鉄、水酸化ランタン等が挙げられる。
特に、銅原子を含有する無機材料は、記録時の熱伝導性の向上、高い感熱発色性を持つことによるコントラストの高い画像の記録、熱源として用いられるレーザー光に対する感度の向上による感熱発色性の向上などの利点が得られるため好ましい。
Specific examples of the metal hydroxide include copper hydroxide, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, antimony hydroxide, cobalt hydroxide, nickel hydroxide, iron hydroxide, and lanthanum hydroxide. .
In particular, inorganic materials containing copper atoms have improved thermal conductivity during recording, recording of images with high contrast due to high thermal color development, and thermal color development due to improved sensitivity to laser light used as a heat source. It is preferable because advantages such as improvement can be obtained.
本発明の積層記録材を構成する感熱発色層としては、前述の感熱発色剤の他、顕色剤その担持体として樹脂、例えば熱可塑性樹脂、熱硬化性樹脂、光硬化性樹脂などの樹脂を使用できる。これらの樹脂は単独で用いてもよく、２種類以上を混合して用いてもよい。 As the thermosensitive coloring layer constituting the laminated recording material of the present invention, in addition to the above-described thermosensitive coloring agent, a resin such as a thermoplastic resin, a thermosetting resin, a photocurable resin, or the like is used as the developer. Can be used. These resins may be used alone or in combination of two or more.
熱可塑性樹脂として具体的には、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂、アクリル系樹脂、ポリ塩化ビニル系樹脂、ポリカーボネート系樹脂、ナイロン系樹脂、ウレタン系樹脂、ポリエステル系樹脂、ＡＢＳ系樹脂、ポリ乳酸系樹脂等が挙げられる。特に、燃焼時のダイオキシン類の発生原因となるハロゲンを含まず、安価で広く市場で使用されているポリプロピレン系樹脂、透明性が高く、リサイクル性の高いポリエステル系樹脂が好ましい。 Specific examples of thermoplastic resins include polyethylene resins, polypropylene resins, polystyrene resins, acrylic resins, polyvinyl chloride resins, polycarbonate resins, nylon resins, urethane resins, polyester resins, ABS resins. And polylactic acid resin. In particular, a polypropylene resin that does not contain a halogen that causes generation of dioxins during combustion, is inexpensive and widely used in the market, and a polyester resin that is highly transparent and highly recyclable is preferable.
熱硬化性樹脂として具体的には、メラミン系樹脂、尿素系樹脂、フェノール系樹脂、エポキシ系樹脂、ウレタン系樹脂、ポリイミド系樹脂、ジアリルフタレート系樹脂、不飽和ポリエステル系樹脂、フラン系樹脂等が挙げられる。 Specific examples of thermosetting resins include melamine resins, urea resins, phenol resins, epoxy resins, urethane resins, polyimide resins, diallyl phthalate resins, unsaturated polyester resins, furan resins, and the like. Can be mentioned.
光硬化性樹脂として具体的には、不飽和ポリエステル系樹脂、アクリレート系樹脂、ポリエン／ポリチオール系樹脂、スピラン系樹脂、エポキシ系樹脂、アミノアルキッド系樹脂、ジアリルフタレート系樹脂、不飽和ポリエステル系樹脂、フラン系樹脂等が挙げられる。これら樹脂と必要に応じて各種モノマー、プレポリマー、光重合開始剤が使用される。 Specific examples of the photo-curable resin include unsaturated polyester resins, acrylate resins, polyene / polythiol resins, spirane resins, epoxy resins, aminoalkyd resins, diallyl phthalate resins, unsaturated polyester resins, Examples include furan resins. These resins and various monomers, prepolymers and photopolymerization initiators are used as required.
感熱発色剤を用いて感熱発色層を形成する場合、発色剤の分散性、各種基材への密着性を考慮するとウレタン樹脂、アクリル樹脂、ポリエステル樹脂、ポリアミド樹脂が好ましい。基材への密着性が弱いと感熱発色時に発色層と剥離し、印字性が低下する問題がある。特に問題となるのは基材がフイルムの場合である。各種フイルムへの密着汎用性も考慮するとウレタン樹脂が特に好ましい。 In the case of forming a heat-sensitive color forming layer using a heat-sensitive color former, urethane resin, acrylic resin, polyester resin, and polyamide resin are preferable in consideration of dispersibility of the color former and adhesion to various substrates. If the adhesion to the substrate is weak, there is a problem that the printability deteriorates due to peeling from the coloring layer during thermal coloring. Particularly problematic is when the substrate is a film. Considering versatility of adhesion to various films, urethane resin is particularly preferable.
本発明の積層記録材は、感熱発色層の上に更に直接、或いは間接的に表面保護層を設け、基材、感熱発色層及び表面保護層の３層からなる積層構造を有していることを特徴とする。表面保護層は大別すると１）感熱発色塗工液を塗布後、乾燥、或いは放射線による硬化で形成する方法、または２）フイルムを直接、或いは接着剤層等を介して感熱発色層と貼り合わせることで形成される方法で得られる。 The laminated recording material of the present invention is provided with a surface protective layer further directly or indirectly on the thermosensitive coloring layer, and has a laminated structure consisting of a base material, a thermosensitive coloring layer and a surface protecting layer. It is characterized by. The surface protective layer can be broadly classified as follows: 1) A method in which a thermosensitive coloring coating solution is applied, followed by drying or curing by radiation, or 2) A film is bonded to the thermosensitive coloring layer directly or via an adhesive layer. It is obtained by the method formed by this.
表面保護層を塗工液から形成する場合、塗工液のバインダー樹脂として、例えば水溶性の、セルロース、メチルセルロース、メトキシセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、ポリビニルアルコール、ポリアクリルアミド、ポリアクリル酸、カゼイン、ゼラチン、スチレン／無水マレイン酸共重合体塩、イソブチレン／無水マレイン酸共重合体塩、ポリアクリル酸エステル、ポリウレタン樹脂、アクリル／スチレン樹脂等が挙げられる。溶剤型樹脂としてはスチレン／マレイン酸、アクリル／スチレン樹脂、ポリスチレン、ポリエステル、ポリカーボネイト、エポキシ樹脂、ポリウレタン樹脂、ポリブチラール樹脂、ポリアクリル酸エステル、スチレン／ブタジエン共重合体、スチレン／ブタジエン／アクリル酸共重合体、ポリ酢酸ビニル等がある。塗工液には、表面保護層の膜強度、耐熱性、耐水性、耐溶剤性等の向上を目的に硬化剤を併用することができる。硬化剤としてはイソシアネート系、オキサゾリン系、カルボジイミド系、エチレンイミン系等が使用できる。膜強度、膜物性の点からはイソシネート系硬化剤が好ましい。イソシアネート系硬化剤の中でも３官能以上のものが特に良好である。 When forming the surface protective layer from the coating liquid, as a binder resin of the coating liquid, for example, water-soluble cellulose, methylcellulose, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyacrylamide, polyacrylic acid, casein, Gelatin, styrene / maleic anhydride copolymer salt, isobutylene / maleic anhydride copolymer salt, polyacrylic acid ester, polyurethane resin, acrylic / styrene resin and the like can be mentioned. Solvent type resins include styrene / maleic acid, acrylic / styrene resin, polystyrene, polyester, polycarbonate, epoxy resin, polyurethane resin, polybutyral resin, polyacrylate ester, styrene / butadiene copolymer, styrene / butadiene / acrylic acid copolymer Examples include polymers and polyvinyl acetate. In the coating liquid, a curing agent can be used in combination for the purpose of improving the film strength, heat resistance, water resistance, solvent resistance and the like of the surface protective layer. As the curing agent, isocyanate, oxazoline, carbodiimide, ethyleneimine, and the like can be used. From the viewpoint of film strength and film physical properties, isocyanate-based curing agents are preferred. Of the isocyanate curing agents, those having 3 or more functional groups are particularly good.
また、表面保護層として放射線硬化型のオーバーコート層を設ける場合、エチレン性不飽和結合を一つ以上有するモノマー、プレポリマーオリゴマー等を用いる。本発明に使用可能なモノマーとしては、Ｎ−ビニルピロリドン、アクリロニトリル、スチレン、アクリルアミド、２−エチルヘキシルアクリレート、２−ヒドロキシ（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、テトラヒドロフルフリルアクリレート、フェノキシエチルアクリレート、ノニルフェノキシエチルアクリレート、ブトキシエチル（メタ）アクリレート、２−ヒドロキシー３−フェノキシプロピルアクリレート、シクロヘキシル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノ（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレートエチル、３−フェノキシプロピルアクリレート、２−メトキシエチル（メタ）アクリレート等の単官能モノマー、エチレングリコールジアクリレート、ジエチレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、テトラエチレングリコールジアクリレート、１，４―ブタンジオールジ（メタ）アクリレート、１，６―ヘキサンジオールジ（メタ）アクリレート、１，１２―ドデカンジオールジ（メタ）アクリレート等の２官能モノマー、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールオクタントリ（メタ）アクリレート、トリメチロールプロパンポリエトキシトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等の３官能モノマー、ペンタエリスリトールポリプロポキシテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート等の４官能モノマー、その他５官能以上のモノマーとしてジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等がある。放射線硬化型組成物としてモノマー、プレポリマー、オリゴマーを用いる場合３官能以上のモノマー、プレポリマー、オリゴマーは２０〜９５重量％以内で使用することが好ましい。２０重量％以下では表面保護層の膜密度、膜強度が低く、場合によっては印字面の平滑性が低下したり、耐水性、耐油性、耐摩耗性等の物性も低下する。９５重量％以上の場合、表面保護層が硬くなり過ぎ印字物を折れ曲げた時、表面保護層の剥離が起こりやすくなる。 When a radiation curable overcoat layer is provided as the surface protective layer, a monomer or prepolymer oligomer having one or more ethylenically unsaturated bonds is used. Examples of monomers that can be used in the present invention include N-vinylpyrrolidone, acrylonitrile, styrene, acrylamide, 2-ethylhexyl acrylate, 2-hydroxy (meth) acrylate, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl acrylate, and phenoxyethyl. Acrylate, nonylphenoxyethyl acrylate, butoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, cyclohexyl (meth) acrylate, N, N-dimethylamino (meth) acrylate, N, N-dimethylaminoethyl (meth) Monofunctional monomers such as ethyl acrylate, 3-phenoxypropyl acrylate, 2-methoxyethyl (meth) acrylate, ethylene glycol diacrylate Diethylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecane Bifunctional monomers such as diol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc. Tetrafunctional monomers such as trifunctional monomers, pentaerythritol polypropoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate Other 5 dipentaerythritol penta (meth) acrylate as a functional or more monomers, dipentaerythritol hexa (meth) acrylate. When monomers, prepolymers, and oligomers are used as the radiation curable composition, it is preferable to use trifunctional or higher functional monomers, prepolymers, and oligomers within 20 to 95% by weight. If it is 20% by weight or less, the film density and film strength of the surface protective layer are low, and the smoothness of the printed surface may be lowered in some cases, and the physical properties such as water resistance, oil resistance, and wear resistance will also be reduced. In the case of 95% by weight or more, the surface protective layer becomes too hard, and when the printed matter is bent, the surface protective layer is easily peeled off.
放射線硬化型組成物には、紫外線で硬化させる場合、光重合開始剤、必要に応じて増感剤が必要となる。光重合開始剤としては、アセトフェノン系、ベンゾフェノン系、チオキサントン系、ベンゾイン系、ベンゾインメチルエーテル系等、増感剤としてはＮ−メチルジエタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｐ−ジメチルアミノ安息香酸イソアミルエステル等のアミン系化合物、トリーｎ−ブチルホスフイン、ミヒラーケトン等を使用することができる。電子線硬化の場合上記の光重合開始剤、増感剤等が使用しなくても硬化させることが可能である。 When the radiation curable composition is cured with ultraviolet rays, a photopolymerization initiator and, if necessary, a sensitizer are required. As photopolymerization initiators, acetophenone series, benzophenone series, thioxanthone series, benzoin series, benzoin methyl ether series, etc. As sensitizers, N-methyldiethanolamine, diethanolamine, triethanolamine, P-dimethylaminobenzoic acid isoamyl ester, etc. Amine compounds, tri-n-butylphosphine, Michler's ketone and the like can be used. In the case of electron beam curing, curing can be performed without using the above-mentioned photopolymerization initiator, sensitizer and the like.
放射線硬化型組成物を硬化させるには、１）紫外線照射として超高圧水銀灯、高圧水銀灯、低圧水銀灯、カーボンアーク燈、メタルハライドランプ等が使用される。２）電子線照射の場合、コックロフトワルトン型、バンデグラフト型、共振変圧器型、絶縁コア変圧器型、或いは、直線型、ダイナミトロン型、高周波型等の各種電子線加速器を用い、１００〜１０００ｅＶのエネルギーを持つ電子を照射する。 In order to cure the radiation curable composition, 1) an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a metal halide lamp, or the like is used for ultraviolet irradiation. 2) For electron beam irradiation, various electron beam accelerators such as Cockloft Walton, Bandegraft, resonant transformer, insulated core transformer, linear type, dynamitron type, high frequency type, etc. Irradiate electrons with energy of 1000 eV.
表面保護層をなす塗工液には、塗工性、皮膜物性向上のため必要に応じて消泡剤、紫外線吸収剤、滑剤、帯電防止剤、硬化剤等の添加剤、また塗工性、印刷適性向上を目的にイソプロピルアルコール、メチルイソブチルケトン、１−メトキシー２―プロパノール、トルエン等の溶剤も使用できる。 In the coating liquid forming the surface protective layer, additives such as an antifoaming agent, an ultraviolet absorber, a lubricant, an antistatic agent, a curing agent, coating properties, Solvents such as isopropyl alcohol, methyl isobutyl ketone, 1-methoxy-2-propanol, and toluene can be used for the purpose of improving printability.
表面保護層がフイルムの場合、通常のプリントラミ、ラミネートに用いられるフイルム、例えば、 ポリエチレン、ポリプロピレン、ポリエステルフイルム等を用いることができる。 In the case where the surface protective layer is a film, it is possible to use a film used for ordinary print lamination or lamination, such as polyethylene, polypropylene, polyester film and the like.
次に積層記録材の生産工程に付いて説明する。感熱発色層及び表面保護層を有する積層記録材の製造は、基本的には１）感熱記録塗工液の調整、２）フイルム、紙への塗布、３）表面保護層の形成により行われる。順次説明すると
１）感熱記録塗工液の調整は次の方法で行うことができる。
感熱発色剤を有機溶剤、水等からなる液状溶媒に分散剤、樹脂を用いて分散する。この場合、塗工液の全成分量に対して発色剤／顕色剤は５〜５０重量％が好ましい。
また芳香環を有するホスホン酸銅を使用する場合、その塗工液中の含有量は０．５〜４０重量％あることが好ましく、２〜３０重量％であることがより好ましい。感熱発色剤の含有量が４０重量％を超えると分散不良を起こしやすく、積層記録材の感熱記録特性を損なう可能性がある。
Next, the production process of the laminated recording material will be described. The production of a laminated recording material having a thermosensitive coloring layer and a surface protective layer is basically carried out by 1) adjustment of a thermosensitive recording coating solution, 2) application to a film or paper, and 3) formation of a surface protective layer. In order, 1) The thermal recording coating solution can be adjusted by the following method.
The heat-sensitive color former is dispersed in a liquid solvent composed of an organic solvent, water and the like using a dispersant and a resin. In this case, the color former / developer is preferably 5 to 50% by weight with respect to the total component amount of the coating liquid.
Moreover, when using the copper phosphonate which has an aromatic ring, it is preferable that content in the coating liquid is 0.5 to 40 weight%, and it is more preferable that it is 2 to 30 weight%. If the content of the heat-sensitive color former exceeds 40% by weight, poor dispersion tends to occur, and the heat-sensitive recording characteristics of the laminated recording material may be impaired.
感熱発色剤を有機溶剤、水等の液状媒体中に分散して塗工液を調製する際に使用する分散機としては、ペイントコンディショナー（レッドデビル社製）、ボールミル、サンドミル（シンマルエンタープライゼス社製「ダイノーミル」等）、アトライター、パールミル（アイリッヒ社製「ＤＣＰミル」等）、コボールミル、ホモミキサー、ホモジナイザー（エム・テクニック社製「クレアミックス」等）、湿式ジェットミル（ジーナス社製「ジーナスＰＹ」、ナノマイザー社製「ナノマイザー」）等が挙げられる。分散機にメディアを使う場合には、ガラスビーズ、ジルコニアビーズ、アルミナビーズ、磁性ビーズ、スチレンビーズ等を用いることが好ましい。 Dispersers used when preparing a coating solution by dispersing a thermosensitive color former in a liquid medium such as an organic solvent or water include paint conditioners (manufactured by Red Devil), ball mills, sand mills (Shinmaru Enterprises) "Dynomill" etc.), Attritor, Pearl Mill ("DCP Mill" manufactured by Eirich), Coball Mill, Homomixer, Homogenizer (such as "Clairemix" manufactured by M Technique), etc., Wet Jet Mill ("Genus" manufactured by Genus) PY ”,“ Nanomizer ”manufactured by Nanomizer, etc.). When using media in the disperser, it is preferable to use glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads, or the like.
２）フイルム、紙への塗布
本発明に用いられる基材としては、フイルム、紙が挙げられる。フイルムとしては低密度ポリエチレン、無延伸および延伸ポリプロピレン、ポリエステル、ナイロン、ポリスチレン、ポリ塩化ビニル、ポリカーボネイト、ポリビニルアルコールフイルム等、及びポリ塩化ビニリデン等をコーテイングしたポリプロピレン、ポリエステル、ナイロン、セロファン等のフイルムも挙げられる。また、蒸着フイルム、例えばシリカなどを蒸着したＰＥＴフイルムも用いることができる。紙としてはアート紙、コート紙、上質紙、和紙、合成紙等が使用できる。
本発明において、感熱発色層の形成はスクリーン印刷、フレキソ印刷、グラビア印刷で行うことが好ましい。塗工液に溶剤を使用している場合、印刷後に乾燥機等により充分乾燥させる必要がある。
３）表面保護層の形成
上記の方法で得られた印刷物は、更に表面保護層を設けることで本発明の一つである積層記録材となる。その積層構成は種々の構成が適用できる。例えば基材がフイルムの場合
（Ａ）フイルム／感熱発色層／フイルム。この場合ラミネートは感熱発色層自体の粘着性により、熱ロール等でラミネートすることができる。感熱発色時の熱、ガス発生等による積層体の剥離、膨れ等を防止するためには接着剤を使用した構成、乃ち（Ｂ）フイルム／感熱発色層／接着剤／フイルムの構成が好適に用いられる。接着剤の使用により表面保護層の剥離、膨れ等が低減できるため、印字、描画した時の鮮明性、コントラストが良好になる。アンカーコート剤でも同様な結果が得られる。
また、印字、描画の基材フイルムに対するコントラスト、美粧性を出すため白インキ、或いは色インキ等の着色インキも同時に印刷することもできる。その場合の構成は（Ｃ）フイルム／感熱発色層／着色インキ層／接着剤／フイルムとなる。この場合、着色インキ層を先に印刷した（Ｄ）フイルム／着色インキ層／感熱発色層／接着剤／フイルムの構成も可能である。（Ｃ）、（Ｄ）構成の使い分けは、使用形態、乃ちどちら側から印字物を見るかによる。その他の構成としてアルミ等のバリア層を有する構成、例えば（Ｅ）フイルム／感熱発色層／接着剤／アルミ／接着剤／フイルム、（Ｆ）シリカ蒸着フイルム／感熱発色層／接着剤／フイルムの構成も可能である。一般的には包装材に供される構成が本発明でも適用可能である。また、表面保護層は塗工液の皮膜からも形成可能である。
基材にフイルムを用いる場合、表面保護層としてフイルムの代わりに塗工液から形成される皮膜を用いることができる。その場合上記の構成例において表面保護層のフイルムを皮膜に変えた構成がそのまま適用できる。この場合基本的には接着剤層は不要である。例えば、（Ａ）、（Ｂ）構成は共にフイルム／感熱発色層／皮膜となる。
2) Application to film and paper Examples of the substrate used in the present invention include film and paper. Examples of films include low density polyethylene, unstretched and stretched polypropylene, polyester, nylon, polystyrene, polyvinyl chloride, polycarbonate, polyvinyl alcohol film, and films such as polypropylene, polyester, nylon, and cellophane coated with polyvinylidene chloride. It is done. Further, a vapor deposition film, for example, a PET film vapor-deposited with silica or the like can also be used. As the paper, art paper, coated paper, high-quality paper, Japanese paper, synthetic paper and the like can be used.
In the present invention, the thermosensitive coloring layer is preferably formed by screen printing, flexographic printing, or gravure printing. When a solvent is used in the coating liquid, it is necessary to sufficiently dry it with a dryer or the like after printing.
3) Formation of surface protective layer The printed matter obtained by the above method becomes a laminated recording material which is one of the present invention by further providing a surface protective layer. Various configurations can be applied to the stacked configuration. For example, when the substrate is a film (A) Film / thermosensitive coloring layer / film. In this case, the laminate can be laminated with a hot roll or the like due to the adhesiveness of the thermosensitive coloring layer itself. In order to prevent exfoliation and swelling of the laminate due to heat, gas generation, etc. during heat-sensitive color development, a configuration using an adhesive, and (B) film / thermo-sensitive color layer / adhesive / film configuration are preferably used. It is done. Since the use of an adhesive can reduce peeling and swelling of the surface protective layer, the sharpness and contrast when printed and drawn are improved. Similar results can be obtained with an anchor coating agent.
Also, white ink or colored inks such as color inks can be printed at the same time in order to give contrast and beauty to the substrate film for printing and drawing. The configuration in that case is (C) film / thermosensitive color developing layer / colored ink layer / adhesive / film. In this case, the structure of (D) film / colored ink layer / thermosensitive color developing layer / adhesive / film in which the colored ink layer is printed first is also possible. (C), (D) The proper use of the configuration depends on the type of usage and on which side the printed material is viewed. Other configurations having a barrier layer such as aluminum, for example, (E) film / thermosensitive color developing layer / adhesive / aluminum / adhesive / film, (F) silica deposited film / thermosensitive color developing layer / adhesive / film Is also possible. In general, a configuration provided for a packaging material is also applicable in the present invention. The surface protective layer can also be formed from a coating liquid coating.
When using a film for the substrate, a film formed from a coating solution can be used as the surface protective layer instead of the film. In that case, the configuration in which the film of the surface protective layer is changed to a film in the above configuration example can be applied as it is. In this case, an adhesive layer is basically unnecessary. For example, the structures (A) and (B) are both film / thermosensitive coloring layer / film.
基材が紙の場合は表面保護層が塗工液を塗布してなる皮膜、或いはフイルムから形成される。その場合の構成として（Ｇ）紙／感熱発色層／皮膜、（Ｈ）紙／感熱発色層／フイルムの構成が好適に用いられる。後者の場合必要に応じて接着剤を介した構成（Ｉ）紙／感熱発色層／接着剤／フイルムが好適に用いられる。
また、印字、描画の基材フイルムに対するコントラスト、美粧性を出すため白インキ、或いは色インキ等の着色インキを先に印刷した（Ｊ）フイルム／着色インキ層／感熱発色層／（接着剤）／フイルムの構成も可能である。一般的には包装材に供される構成が本発明でも適用可能である。
When the substrate is paper, the surface protective layer is formed from a film or film formed by applying a coating solution. As the constitution in that case, the constitution of (G) paper / thermosensitive coloring layer / film and (H) paper / thermosensitive coloring layer / film is preferably used. In the latter case, the constitution (I) paper / thermosensitive color developing layer / adhesive / film through an adhesive is suitably used as necessary.
In addition, a white ink or a colored ink such as a color ink is printed first in order to give a contrast to the base film for printing and drawing, and a cosmetic property. (J) Film / colored ink layer / thermosensitive color developing layer / (adhesive) / A film configuration is also possible. In general, a configuration provided for a packaging material is also applicable in the present invention.
表面保護層にフイルムを用いる場合、フイルムのラミネート方法としては１）印刷を施したフイルム若しくは紙に溶剤型接着剤を塗布し、溶剤を乾燥させた後にフイルム等を貼り合わせるドライラミネーション、２）印刷を施したフイルム若しくは紙にアンカーコート剤を塗布、乾燥し、ポリエチレン、ポリプロピレン等の溶融樹脂を積層したり、若しくは該溶融樹脂を介在して他のフイルムを積層する溶融押し出し、３）印刷を施したフイルム若しくは紙に無溶剤型接着剤を加熱下で塗布しフイルム又は金属箔を張り合わせるノンソルラミネーションが挙げられる。何れのラミネーションも可能であるが積層記録材の加熱時におけるガス発生、膨れ等を防ぐために接着剤層が厚いドライラミネーションがより好ましい。また、表面保護層にフイルムを用いる場合、該フイルムと感熱接着剤層を前もって積層した積層フイルムを感熱発色層に貼り合わせることでも積層記録材を形成できる。この方法は基材に紙を用いた場合好適に用いられる。 When a film is used for the surface protective layer, the film lamination method is as follows: 1) Dry lamination in which a solvent-type adhesive is applied to the printed film or paper, the solvent is dried, and then the film is pasted. 2) Printing Apply the anchor coating agent to the coated film or paper, dry it, and laminate a molten resin such as polyethylene or polypropylene, or melt extrude that laminates another film with the molten resin in between, 3) perform printing Non-solumination may be mentioned in which a solvent-free adhesive is applied to a film or paper under heating and a film or metal foil is laminated. Any lamination is possible, but dry lamination with a thick adhesive layer is more preferable in order to prevent gas generation and swelling during heating of the laminated recording material. When a film is used for the surface protective layer, a laminated recording material can also be formed by laminating a laminated film obtained by previously laminating the film and a heat-sensitive adhesive layer to the heat-sensitive color developing layer. This method is preferably used when paper is used as the substrate.
本発明に用いられる接着剤としては、水性接着剤、溶剤型接着剤若しくは無溶剤型接着剤が挙げられる。水性接着剤としてはポリウレタン樹脂系、ポリ酢酸ビニルエマルジョン系、アクリルエマルジョン系、エポキシエマルジョン系等がある。必要に応じて水系の硬化剤例えば、イソシアネートエマルジョン、カルボジイミドエマルジョンを併用することができる。溶剤型としてはポリウレタン樹脂系、アクリル樹脂系の１液若しくは２液型接着剤、ポリイソシアネート／ポリエーテル系、ポリイソシアネート／ポリエステル系の２液接着剤がある。無溶剤型接着剤としてはポリエチレン、ポリプロピレン系がある。
また、アンカーコート剤としてポリエステル／イソシア系、ポリエーテル／イソシア系、エチレンイミン系、ブタジエン系、チタネート系を使用することができる。これらアンカーコート剤は印刷を施した面にグラビアコータ、ロールコータ等で塗布される。
Examples of the adhesive used in the present invention include a water-based adhesive, a solvent-type adhesive, and a solventless adhesive. Examples of the aqueous adhesive include polyurethane resin, polyvinyl acetate emulsion, acrylic emulsion, and epoxy emulsion. If necessary, an aqueous curing agent such as an isocyanate emulsion or a carbodiimide emulsion can be used in combination. Examples of the solvent type include polyurethane resin-based and acrylic resin-based one-component or two-component adhesives, polyisocyanate / polyether-based, and polyisocyanate / polyester-based two-component adhesives. Solventless adhesives include polyethylene and polypropylene.
Further, polyester / isocyanate, polyether / isocyanate, ethyleneimine, butadiene, and titanate can be used as the anchor coating agent. These anchor coating agents are applied to the printed surface with a gravure coater, a roll coater or the like.
食品包装用としては、印刷時に包装材の一部分に感熱発色インキを印刷することにより、部分的に印字可能な包装材料を得ることができる。こうして得られた包装材料には、賞味期限、ロット番号等を個別に印刷することも可能となる。 For food packaging, a partially printable packaging material can be obtained by printing a thermosensitive color ink on a part of the packaging material during printing. It is also possible to individually print the expiration date, lot number, etc. on the packaging material thus obtained.
次に、積層記録材を用いた感熱記録方法について説明する。
感熱記録は、感熱発色層及び表面保護層を有する積層記録材に、加熱により記録することによって行う。印字は感熱発色層をなす１）発色剤／顕色剤、或いは２）芳香環を有するホスホン酸銅が熱により化学的に結合し、発色（１の場合）、酸化分解または炭化する（２の場合）ことで行われる。後者の場合、素材によっては芳香環を有するホスホン酸銅の周りに存在する樹脂等の担持体も熱により分解し変色することで、非常に鮮明なコントラストを持った記録を行うことができる。他の発色剤、例えば銅、モリブデン複合酸化物等も同様に周りの樹脂等を熱分解し、鮮明な記録を可能とする。記録する際のエネルギー量は、芳香環を有するホスホン酸銅の種類や量、記録部分の厚みなどによって異なるが、少なくとも芳香環を有するホスホン酸銅が酸化分解または炭化するためのエネルギー量は必要であり、記録時の加熱温度は２５０〜５５０℃であることが好ましく、３００〜５００℃であることがより好ましい。
Next, a thermal recording method using a laminated recording material will be described.
Thermal recording is performed by recording on a laminated recording material having a thermal coloring layer and a surface protective layer by heating. Printing forms a heat-sensitive color developing layer 1) Color former / developer, or 2) Copper phosphonate having an aromatic ring is chemically bonded by heat, and develops color (in the case of 1), oxidative decomposition or carbonization (2) Case). In the latter case, depending on the material, a carrier such as a resin existing around copper phosphonate having an aromatic ring is also decomposed and discolored by heat, so that recording with a very clear contrast can be performed. Other color formers, such as copper and molybdenum composite oxides, similarly, thermally decompose the surrounding resin and enable clear recording. The amount of energy for recording varies depending on the type and amount of copper phosphonate having an aromatic ring, the thickness of the recording portion, etc., but at least the amount of energy required for oxidative decomposition or carbonization of copper phosphonate having an aromatic ring is necessary. The heating temperature during recording is preferably 250 to 550 ° C, more preferably 300 to 500 ° C.
感熱記録を行う加熱源としては、例えばサーマルヘッド、熱ペン、レーザー光等が挙げられる。サーマルヘッドや熱ペンを用いる場合は、熱伝導率の高い無機材料、カーボンブラック、グラファイトを、芳香環を有するホスホン酸銅と一緒に用いることが好ましい。また、レーザー光を用いる場合は、熱伝導率が高く、使用するレーザー光に対しても感度を有する無機材料、カーボンブラック、グラファイトを、芳香環を有するホスホン酸銅と一緒に用いることが好ましい。レーザー光としては、例えば炭酸ガスレーザー、ＹＡＧレーザー、ＹＶＯ４レーザー、エキシマレーザー等が挙げられる。 Examples of the heat source for performing thermal recording include a thermal head, a thermal pen, and laser light. When using a thermal head or a thermal pen, it is preferable to use an inorganic material having high thermal conductivity, carbon black, or graphite together with copper phosphonate having an aromatic ring. In the case of using laser light, it is preferable to use an inorganic material having high thermal conductivity and sensitivity to the laser light used, carbon black, and graphite together with copper phosphonate having an aromatic ring. Examples of the laser light include a carbon dioxide laser, a YAG laser, a YVO4 laser, and an excimer laser.
レーザーマーキングを行う場合、レーザー光は、感熱発色層に吸収、散乱がより低減される側より照射される。例えば（Ｄ）フイルム／着色インキ層／感熱発色層／接着剤／フイルム構成の場合、表面保護層のフイルム側から照射することが好ましい。 When performing laser marking, laser light is irradiated from the side where absorption and scattering are further reduced in the thermosensitive coloring layer. For example, in the case of (D) film / colored ink layer / thermosensitive coloring layer / adhesive / film structure, it is preferable to irradiate from the film side of the surface protective layer.
[実施例]
以下、実施例に基づき本発明をさらに詳しく説明するが、本発明は実施例に限定されるものではない。実施例中、部および％は、重量部および重量％をそれぞれ表す。
（合成例１）フェニルホスホン酸銅の合成
水１３５０部に、フェニルホスホン酸１３０部を溶解させた。これに、硫酸銅５水和物１０３部を添加し、室温下で２時間攪拌した。析出物をろ過し、水で洗浄を行い、１００℃で減圧乾燥させフェニルホスホン酸銅３５部を得た。
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited to an Example. In the examples, parts and% represent parts by weight and% by weight, respectively.
(Synthesis Example 1) Synthesis of copper phenylphosphonate 130 parts of phenylphosphonic acid was dissolved in 1350 parts of water. To this, 103 parts of copper sulfate pentahydrate was added and stirred at room temperature for 2 hours. The precipitate was filtered, washed with water, and dried under reduced pressure at 100 ° C. to obtain 35 parts of copper phenylphosphonate.
（合成例２）４−エチルフェニルホスホン酸銅の合成
フェニルホスホン酸の代わりに４−エチルフェニルホスホン酸１５３部を使用した以外は合成例１と同様にして４−エチルフェニルホスホン酸銅を得た。
(Synthesis Example 2) Synthesis of copper 4-ethylphenylphosphonate Copper 4-ethylphenylphosphonate was obtained in the same manner as in Synthesis Example 1 except that 153 parts of 4-ethylphenylphosphonic acid was used instead of phenylphosphonic acid. .
（合成例３）ウレタン樹脂の合成
攪拌機、温度計、還流冷却器、および窒素ガス導入管を備えた四つ口フラスコにアジピン酸と３−メチルー１，５―ペンタンジオールから得られる分子量２，０００のポリエステルジオール１，０００部とイソホロンジイソシアネート２２２部を仕込み、窒素雰囲気下、８５℃で５時間反応させた。次いで、４０℃に冷却後イソホロンジアミン８２部、ジ−ｎ−ブチルアミン７．８部、トルエン１，２４４部、メチルエチルケトン１，２４４部およびイソプロピルアルコール５７３部を添加し、攪拌下４０℃で５時間反応させた。このようにして得られたウレタン樹脂の固形分は３０％、粘度は３５０ｃｐｓ（２５℃）であった。
(Synthesis Example 3) Synthesis of Urethane Resin A molecular weight of 2,000 obtained from adipic acid and 3-methyl-1,5-pentanediol in a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas introduction tube 1,000 parts of polyester diol and 222 parts of isophorone diisocyanate were charged and reacted at 85 ° C. for 5 hours in a nitrogen atmosphere. Next, after cooling to 40 ° C., 82 parts of isophorone diamine, 7.8 parts of di-n-butylamine, 1,244 parts of toluene, 1,244 parts of methyl ethyl ketone and 573 parts of isopropyl alcohol were added and reacted at 40 ° C. for 5 hours with stirring. I let you. The urethane resin thus obtained had a solid content of 30% and a viscosity of 350 cps (25 ° C.).
（合成例４）アクリル樹脂の合成
攪拌機、温度計、還流冷却器、および窒素ガス導入管を備えた四つ口フラスコにイソプロピルアルコール６００部を仕込み、攪拌下、窒素雰囲気下で８０℃迄昇温した。次に、予め調整して置いたアクリル酸４８部、メタクリル酸メチル４２０部、アクリル酸ブチル１３２部およびアゾビスイソブチロニトリル１２部の混合液を２時間で滴下した。滴下後１時間経て、アゾビスイソブチロニトリル２部を加え、更に２時間反応させた。反応終了後、メチルエチルケトンで固形分の調整を行った。このようにして得られたアクリル樹脂の固形分は３０％、粘度は３５０ｃｐｓ（２５℃）であった。
(Synthesis Example 4) Synthesis of acrylic resin A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas introduction tube was charged with 600 parts of isopropyl alcohol, and the temperature was raised to 80 ° C. in a nitrogen atmosphere with stirring. did. Next, a mixed solution of 48 parts of acrylic acid, 420 parts of methyl methacrylate, 132 parts of butyl acrylate and 12 parts of azobisisobutyronitrile prepared in advance was dropped over 2 hours. One hour after the dropping, 2 parts of azobisisobutyronitrile was added, and the mixture was further reacted for 2 hours. After completion of the reaction, the solid content was adjusted with methyl ethyl ketone. The acrylic resin thus obtained had a solid content of 30% and a viscosity of 350 cps (25 ° C.).
（合成例５）水性アクリル樹脂の合成
攪拌機、温度計、還流冷却器、および窒素ガス導入管を備えた四つ口フラスコにイソプロピルアルコール６００部を仕込み、攪拌下、窒素雰囲気下で８０℃迄昇温した。次に、予め調整して置いたアクリル酸４８部、メタクリル酸メチル４２０部、アクリル酸ブチル１３２部およびアゾビスイソブチロニトリル１２部の混合液を２時間で滴下した。滴下後１時間経て、アゾビスイソブチロニトリル２部を加え、更に２時間反応させた。反応終了後に５０℃に冷却し、ジメチルエタノールアミン４５部を加え、充分に攪拌した。更にイオン交換水を添加し、昇温を行い、脱溶剤を行った。このようにして得られた水性アクリル樹脂（Ｃ）の固形分は３０％、粘度は４００ｃｐｓ（２５℃）、ｐＨ＝７．９であった。
(Synthesis Example 5) Synthesis of water-based acrylic resin A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas introduction tube was charged with 600 parts of isopropyl alcohol, and the temperature was raised to 80 ° C. with stirring under a nitrogen atmosphere. Warm up. Next, a mixed solution of 48 parts of acrylic acid, 420 parts of methyl methacrylate, 132 parts of butyl acrylate and 12 parts of azobisisobutyronitrile prepared in advance was dropped over 2 hours. One hour after the dropping, 2 parts of azobisisobutyronitrile was added, and the mixture was further reacted for 2 hours. After completion of the reaction, the mixture was cooled to 50 ° C., 45 parts of dimethylethanolamine was added, and the mixture was sufficiently stirred. Further, ion exchange water was added, the temperature was raised, and the solvent was removed. The aqueous acrylic resin (C) thus obtained had a solid content of 30%, a viscosity of 400 cps (25 ° C.), and a pH = 7.9.
表面保護層をなす塗工液としてＵＶニスを用いた。ＵＶニスの組成を示すと
ＵＶニス１：ペンタエリスリトールヘキサアクリレート３部／ペンタエリスリトールトリアクリレート３部／トリプロピレングリコールジアクリレート３０部／３−フェノキシプロピルアクリレート８部／イルガキュアー１８４（チバガイギー社製）６部／ＩＰＡ５０部
ＵＶニス２：ペンタエリスリトールヘキサアクリレート２０部／ペンタエリスリトールトリアクリレート１０部／トリプロピレングリコールジアクリレート８部／３−フェノキシプロピルアクリレート６部／イルガキュアー１８４（チバガイギー社製）６部／ＩＰＡ５０部
ＵＶニス３：ペンタエリスリトールヘキサアクリレート２５部／ペンタエリスリトールトリアクリレート１７部／トリプロピレングリコールジアクリレート１部／３−フェノキシプロピルアクリレート１部／イルガキュアー１８４（チバガイギー社製）６部／ＩＰＡ５０部
UV varnish was used as a coating solution for forming the surface protective layer. The composition of the UV varnish is as follows: UV varnish 1: pentaerythritol hexaacrylate 3 parts / pentaerythritol triacrylate 3 parts / tripropylene glycol diacrylate 30 parts 3-phenoxypropyl acrylate 8 parts / Irgacure 184 (manufactured by Ciba Geigy) 6 Parts / IPA 50 parts UV varnish 2: pentaerythritol hexaacrylate 20 parts / pentaerythritol triacrylate 10 parts / tripropylene glycol diacrylate 8 parts / 3-phenoxypropyl acrylate 6 parts / Irgacure 184 (Ciba Geigy) 6 parts / IPA50 Parts UV varnish 3: 25 parts of pentaerythritol hexaacrylate / 17 parts of pentaerythritol triacrylate / 1 part of tripropylene glycol diacrylate / 3-pheno Shi acrylate 1 part / Irgacure 184 (manufactured by Ciba-Geigy) 6 parts / IPA50 parts
実施例３
発色剤としてフェニルホスホン酸銅１００部、樹脂としてウレタン樹脂２００部をプレミックスし、ペイントシェーカ（ガラスビーズ使用）にて５時間分散した。次にウレタン樹脂２００部、およびメチルエチルケトンを加え、固形分３０％に調整した。こうして得られたインキをメチルエチルケトンで一律に５０％希釈し、グラビア印刷用の感熱発色インキとした。印刷、ラミネートは実施例１と同様である。
実施例４〜１５
用いた１）感熱発色インキを成す発色剤、添加剤および樹脂、２）印刷における基材フイルム、３）ラミネートにおけるラミネートの方法およびシーラントフイルムについて表１に記す。尚、実施例５〜８については添加剤ＡＴＯ２０部、カーボンブラック１部、グラファイト１部、炭酸銅２０部を添加した。
実施例１６
実施例３で得た印刷物に溶剤型のＯＰニス（ニトロセルロース系）を塗工、乾燥により、表面保護層を形成し、積層記録材を得た。
Example 3
100 parts of copper phenylphosphonate as a color former and 200 parts of urethane resin as a resin were premixed and dispersed for 5 hours with a paint shaker (using glass beads). Next, 200 parts of urethane resin and methyl ethyl ketone were added to adjust the solid content to 30%. The ink thus obtained was uniformly diluted 50% with methyl ethyl ketone to obtain a heat-sensitive color ink for gravure printing. Printing and laminating are the same as in Example 1.
Examples 4-15
Table 1 shows the used 1) color formers, additives and resins constituting the heat-sensitive color ink, 2) the base film in printing, 3) the laminating method and the sealant film in the laminate. In Examples 5 to 8, 20 parts of additive ATO, 1 part of carbon black, 1 part of graphite, and 20 parts of copper carbonate were added.
Example 16
The printed matter obtained in Example 3 was coated with a solvent-type OP varnish (nitrocellulose-based) and dried to form a surface protective layer to obtain a laminated recording material.
実施例１７〜１９
用いた１）感熱発色インキを成す発色剤、添加剤および樹脂、２）印刷における紙、３）ＵＶニスについて表１に記す。ＵＶニスを塗布、乾燥した。引き続きUV照射は８０Ｗ／ｃｍの高圧水銀灯下１０ｃｍの距離で、コンベア速度１０ｍ／分で２パス通し、積層記録材を得た。
実施例２０
実施例３で得た印刷物に溶剤型エチレン−酢酸ビニル共重合体接着剤を塗布、乾燥してＯＰＰを貼り合わせ積層記録材を得た。
比較例１ 実施例３の印刷物をそのまま記録材として用いた。この記録材の感熱発色層は皮膜、フイルムで保護されていない。
Examples 17-19
Table 1 shows the 1) color formers, additives and resins forming the heat-sensitive color ink, 2) paper for printing, and 3) UV varnish. UV varnish was applied and dried. Subsequently, UV irradiation was performed at a distance of 10 cm under a high-pressure mercury lamp of 80 W / cm and two passes at a conveyor speed of 10 m / min, to obtain a laminated recording material.
Example 20
A solvent-type ethylene-vinyl acetate copolymer adhesive was applied to the printed matter obtained in Example 3 and dried, and OPP was laminated to obtain a laminated recording material.
Comparative Example 1 The printed material of Example 3 was used as a recording material as it was. The thermosensitive coloring layer of this recording material is not protected by a film or film.
上記の方法で得られた積層記録材についてサーマルヘッド、レーザーによる印字試験を行い、印字物のＯ．Ｄ．値を評価した。また、印字物に対して加熱によるフイルムの表面状態、特に膨れ性（加熱側のフイルム表面）を目視で評価した。
（記録方法Ａ）
得られた積層記録材について、ドット密度８ドット／ｍｍ、ヘッド抵抗１３００Ωの大倉電機社製サーマルヘッド「ＴＨ−ＰＭＤ」を具備するＧIIIＦＡＸ試験機を使用して、感熱記録を行った。記録は、ヘッド電圧２２Ｖ、通電時間１．２ｍｓで行い、記録画像の反射濃度（Ｏ．Ｄ.値）をマクベス濃度計で測定した。感熱記録した結果を表２に示す。
The laminated recording material obtained by the above method was subjected to a printing test using a thermal head and a laser, and the O.D. D. The value was evaluated. Moreover, the surface state of the film by heating with respect to the printed matter, particularly the swelling property (film surface on the heating side) was visually evaluated.
(Recording method A)
The obtained laminated recording material was subjected to thermal recording using a GIIIFAX testing machine equipped with a thermal head “TH-PMD” manufactured by Okura Electric Co., Ltd. having a dot density of 8 dots / mm and a head resistance of 1300Ω. Recording was performed at a head voltage of 22 V and an energization time of 1.2 ms, and the reflection density (OD value) of the recorded image was measured with a Macbeth densitometer. The results of thermal recording are shown in Table 2.
（記録方法Ｂ）
得られた積層記録材について、ＹＶＯ４レーザー「ＹＶＯ社製ｉ-Ｍａｒｋｅｒ１０Ｗ」（連続描画）を使用して感熱記録を行い、記録画像の反射濃度（Ｏ．Ｄ.値）をマクベス濃度計で測定した。感熱記録した結果を表２に示す。
(Recording method B)
The obtained laminated recording material was subjected to thermal recording using a YVO4 laser “i-Marker10W manufactured by YVO” (continuous drawing), and the reflection density (OD value) of the recorded image was measured with a Macbeth densitometer. . The results of thermal recording are shown in Table 2.
表面状態（膨れ性）：３段階で評価した。結果を表２に示す。
○：加熱側の表面に膨れが全くない。結果は表２にまとめた。
△： 〃 僅かに見られる
×： 〃 甚だしい。
Surface condition (swelling property): Evaluated in three stages. The results are shown in Table 2.
○: There is no swelling on the surface on the heating side. The results are summarized in Table 2.
Δ: 〃 Slightly observed ×: 〃 Severe.
耐溶剤性：印字後に、積層記録材の印字側をメチルエチルケトンを含浸させた脱脂面で１０回ラビングを行い、その表面状態を評価した。結果は表２にまとめた。
○：加熱側の印字表面が全く取れない。
△： 〃 僅かに取られる
×： 〃 甚だしく取られる。
Solvent resistance: After printing, the printing side of the laminated recording material was rubbed 10 times with a degreased surface impregnated with methyl ethyl ketone, and the surface condition was evaluated. The results are summarized in Table 2.
A: The print surface on the heating side is not removed at all.
Δ: 〃 Slightly removed ×: 〃 Severely removed
Claims (15)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
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| JP2004256565A JP4356564B2 (en) | 2004-09-03 | 2004-09-03 | Laminated recording material |
| EP05781408A EP1800885B1 (en) | 2004-09-03 | 2005-09-02 | Recording material and method of recording |
| US11/661,676 US8461075B2 (en) | 2004-09-03 | 2005-09-02 | Recording material and method of recording |
| PCT/JP2005/016143 WO2006030654A1 (en) | 2004-09-03 | 2005-09-02 | Recording material and method of recording |
| DE602005022901T DE602005022901D1 (en) | 2004-09-03 | 2005-09-02 | RECORD MATERIAL AND RECORDING PROCEDURE |
| AT05781408T ATE477127T1 (en) | 2004-09-03 | 2005-09-02 | RECORDING MATERIAL AND RECORDING METHODS |
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| JP2004256565A JP4356564B2 (en) | 2004-09-03 | 2004-09-03 | Laminated recording material |
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| JP4356564B2 true JP4356564B2 (en) | 2009-11-04 |
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| JP2006076210A (en) * | 2004-09-10 | 2006-03-23 | Toyo Ink Mfg Co Ltd | Expanded recording material and expansion recording method |
| ATE477127T1 (en) | 2004-09-03 | 2010-08-15 | Toyo Ink Mfg Co | RECORDING MATERIAL AND RECORDING METHODS |
| JP5144942B2 (en) * | 2007-02-21 | 2013-02-13 | 東洋インキＳｃホールディングス株式会社 | Laser beam coloring sheet |
| JP5023799B2 (en) * | 2007-05-11 | 2012-09-12 | 東洋インキＳｃホールディングス株式会社 | Laser coloring laminate |
| JP5157380B2 (en) * | 2007-11-13 | 2013-03-06 | 大日本印刷株式会社 | LAMINATE FOR LASER PRINTING AND LASER PRINTING METHOD |
| JP5343403B2 (en) * | 2008-05-28 | 2013-11-13 | Ｄｉｃ株式会社 | Adhesive film for laminating and laser marking label |
| JP5681400B2 (en) * | 2010-07-07 | 2015-03-04 | Dic株式会社 | Resin composition for heat-sensitive recording medium protective layer and heat-sensitive recording medium using the same |
| JP6482356B2 (en) * | 2015-03-31 | 2019-03-13 | 日本カーバイド工業株式会社 | Laser label and laser marking method using the same |
| JP7360783B2 (en) * | 2018-02-27 | 2023-10-13 | 大日本印刷株式会社 | Packaging materials, packaging containers, lids and labels |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2938467B2 (en) * | 1989-03-09 | 1999-08-23 | 三井化学株式会社 | Optical recording medium |
| JPH07323662A (en) * | 1994-06-01 | 1995-12-12 | Toppan Printing Co Ltd | Thermal recording material |
| JP3465766B2 (en) * | 1995-06-23 | 2003-11-10 | 大日精化工業株式会社 | Ink composition for laser thermal recording |
| JPH1178243A (en) * | 1997-09-16 | 1999-03-23 | Tomoegawa Paper Co Ltd | Thermal recording material |
| JPH11254831A (en) * | 1998-01-09 | 1999-09-21 | Ricoh Co Ltd | Thermal recording material |
| JPH11240251A (en) * | 1998-02-26 | 1999-09-07 | Oji Paper Co Ltd | Thermal recording material |
| JP2000127641A (en) * | 1998-10-22 | 2000-05-09 | Fuji Photo Film Co Ltd | Thermosensitive image forming material and lithographic original plate |
| US6207344B1 (en) * | 1999-09-29 | 2001-03-27 | General Electric Company | Composition for laser marking |
| JP2001096916A (en) * | 1999-10-01 | 2001-04-10 | Toshiba Tec Corp | Heat-sensitive printing medium and thermal printer |
| JP4269936B2 (en) * | 2003-12-26 | 2009-05-27 | 東洋インキ製造株式会社 | Thermal recording composition and use thereof |
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